Aryloxy acid urethane and method of preparing same



United States Patent ARYLOXY ACID URETHANE AND METHOD OF PREPARING SAMEAlfred W. Breiner, Racine, Wis., assignor to S. C. Johnson & Son, Inc.,Racine, Wis.

N0 Drawing. Application August 6, 1956 Serial No. 602,460

7 Claims. ('Cl. 260-25) This invention relates to new urethane-modifiedsynthetic resins possessing outstanding hardness, combined withtoughness, and superior chemical resistance. More particularly, itrelates to reaction products of resinous aryloxy acids and isocyanatewith a substantial amount of the latter containing two or moreisocyanate groups per molecule. These reactants may be formulated andapplied so as to give exceedingly hard, tough, chemically resistantprotective coating films and adhesives, or they may be formulated andapplied so as to give low density, foamed cellular plastics of tough,rigid structure.

An object of this invention is the formulation of admixtures of thearyloxy acids and isocyanates which on further reaction forminsoluble,infusible compositions and products.

Another object of this invention is the formulation of urethane-modifiedresinous aryloxy acid compositions which are hard, extremely toughproducts, possessing good chemical and water resistance.

A further object of this invention is the formulation ofurethane-modified resinous aryloxy acid compositions which are lowdensity, tough, rigid, cellular products.

Other objects of the invention will appear from the following moredetailed description, with particular reference to the specificillustrative examples.

The resinous aryloxy acids used in this invention are prepared, asdescribed in the copending Greenlee application, Serial No. 403,645,filed January 12, 1954, by reacting in the presence of alkali a dihydricphenol with a coupling agent having two functional groups which readilyform ether linkages with phenolic hydroxyl groups. The amount ofdihydric phenol used is in excess of the equivalent amount of thecoupling agent so as to provide unreacted phenolic hydroxyl groups inthe product. A part of the unreacted phenolic hydroxyl groups are thenetherified in the presence of alkali with a substituted carboxylic acid.The final product is thus an aryloxy acid containing a plurality ofether oxygens and conforming to the general formula:

where 'A is an arylene radical, R is a divalent aliphatic radical having21() carbon atoms, R is a divalent ali-.

phatic hydrocarbon radical of 1 to 7 carbon atoms and n has a value of 1to and wherein (A) and (B) are 2,890,181 Patented June 9, 1959 presentin amounts having a ratio on an equivalent weight basis of 5:1 to 1:3.

The dihydric phenols suitable for use in making the aryloxy acids may bemononuclear such as resorcinol, hydroquinone, catechol, etc., orpolynuclear, such as p,p-dihydroxy benzophenone, p,p'-dihydroxydiphenyl, p,p'dihydroxy dibenzyl, dihydroxy anthracenes, dihydroxynaphthalenes, bisphenols wherein the aromatic nuclei are joined by analkyl group having from 1 to 10 carbon atoms, etc. Particularlyadvantageous in making the aryloxy acids herein described are thebisphenols.

The coupling agents advantageously used in building up the molecularstructure desired for the resinous aryloxy monoacids are bifunctional intheir reactions with the dihydric phenols in the presence of alkali.Epichlorohydrin is bifunctional in such reactions in that the epoxidegroup and the chloride group each react with a phenolic hydroxyl groupin the presence of alkali, forming ether linkages between theepichlorohydrin residue and the dihydric phenol residue. Epihalohydrinsother than epichlorohydrin, such as epibromohydrin and those structuresin which one of the carbon atoms is replaced by an ether,

oxygen such as 2,3-epoxypropyl-2-hydroxy3Gchloropropyl ether may beused. The epihalohydrins suitable for use as coupling agents should bebased on an aliphatic structure containing from 3 to 10 carbon atoms.Similarly, diepoxides containing 4 to 10 carbon atoms such as1,2-epoxy-3,4-epoxybutane, or those in which one of the carbon atoms isreplaced by an ether oxygen such as bis(2,3-epoxypropyl)ether may beused. Epoxid'es referred to herein are limited to those in which theoxygen bridges adjacent carbon atoms, also referred to as ethyleneoxides.

The coupling agent may also be an aliphatic dihalide since thesematerials also react with phenolic hydroxyl groups to form ethers.Exemplary halides'are 1,2-dichloroethane, 1,3-dichloropropane,1,2-dibromoethane; 1,3-dibromopropane, 1,10-dichlorodecane, and thedihalides of corresponding olefins. The ethers of the dihalides may alsobe used in this capacity. Such dihalo ethers are dichloroethylether,dichloroisopropyl ether,"

dichloroethyl formal, and triglycol dichloride.

The substituted carboxyl'ic acids suitable for use in the preparation ofthe resinous aryloxy monoacids are those which contain up to about 8carbon atoms and-a.

single functional group which is capable of reacting with phenolichydroxyl groups to form an ether. Exemplary acids are the monohalo acidssuch as chloroacetic acid, 2-chlorocaprylic acid, S-bromovaleric acid,etc.

The successive reactions leading to a typical aryloxy acid prepared fromp,p'-isopropylidenediphenol,

The reaction of 3 mols of p,p-isopropylidenediphenol with 2 mols of his(beta-chloroethyl) ether and 1 mol of chloroacetic acid would berequired to give the following structure:

It is understood that in the illustrative reactions given above, thedesired products may be obtained in predominant amounts by properlyadjusting the molar proportions "of materials and the reactionconditions, but the formation of products of side reactions cannot beavoided in all cases. In the preparation of the resinous monoacids, ithas been found that the side reaction products are usually not presentto such a degree as to be detrimental to the properties of the finalurethane composition; Where side products are found to be present to anappreciable extent, it is possible to separate the same in the. courseof preparing the resinous acid. Such a separation is illustrated inExample II which involves the removal of the unreactedp,p'-isopropylidenediphenol after its reaction with epichlorohydrin andbefore the addition of chloroacetic acid to form the final aryloxymonoacids.

It will be noted that where the aliphatic coupling agent containsalcoholic hydroxyl groups, e.g. 1,3-dichloropropanol-2, and in caseswhere at least one of the coupling functions is an epoxide group as inepichlorohydrin, the resinous aryloxy acid will contain one or morealcoholic hydroXyl groups per molecule in addition to the phenolichydroxyl group and the carboxyl group. With other coupling agents, suchas bis(2-chloroethy1)ether and 1,4- dichlorobutane, the functionalgroups present in the final structure are primarily phenolic hydroxylgroups and carboxyl groups. In the latter instance there would be minorportions of alcoholic hydroxyl groups from the side reaction ofhydrolysis of some alkyl halide. The method used for determining therelative portions of alcoholic and phenolic hydroxyl groups in theproducts containing both functions is described in Quantitative OrganicAnalysis Via Functional Groups by Sidney Siggia,

4 pp. 4-8, published by John Wiley & Sons, Inc., New York, New York(1949).

The isocyanates used for reaction with the resinous aryloxy acids arecompounds with the general formula R(NCX) where X may be oxygen orsulfur, z an integer, one or more, and R an organic radical. Theseisocyanates, therefore, may be either aromatic or aliphatic or mixedaromatic, aliphatic products. Although it is necessary to have more than50% of z in these reactions equal to at least two to promotepolymerization, monofunctional compounds are often desirable to modifythe product. This is especially true in compositions giving a highdegree of crosslinking, and in such a manner limiting the flexibility orcausing premature gelation. The mono-isocyanates in such instances wouldserve to decrease the degree of cross-linking and thereby reduce thepossibility of gelation and also give a more fiexible film.

Preferred isoeyanates for use in this invention are toluene 2,4diisocyanate, toluene 2,6 diisocyanate, methylenebis(4-phenyl-isocyanate), 3,3bitolylene 4,4diisocyanate,hexarnethylene-diisocyanate, and octadecylisocyanate. This preference isbased on the commercial availability of such compounds. However, anycompound of the general formula R(NCX) as described above, may be used.This invention thus includes the use of ethylene diisocyanate,trimethylene diisocyanate, tetramethylene diisocyanate, decamethylenediisocyanate, heptylidene diisocyanate and the correspondingdiisothiocyanates; cycloalkylene diisocyanates and diisothiocyanates,e.g. cyclopentylene diisocyanate, cyclohexylene diisocyanate; aromaticdiisocyanates and diisothiocyanates, e.g. m-phenylene diisocyanate,naphthalene diisocyanate and diphenyl- 4,4-diisocyanate;aliphatic-aromatic diisocyanates and diisothiocyanates, e.g.xylene-1,4-diisocyanate and 4,4- diphenylenemethane diisocyanate; andheterocyclic diisocyanates, and diisocyanates such as SCNCH OCH NCS andSCN(CH S(CH NCS; the isocyanates and isothiocyanates containing morethan two functional groups, e.g. benzene 1,2,4-triisothiocyanate,1,2,2-triisocyanatobutane, toluene triisocyanate; and as modifiers, themonoisocyanates and monothioisocyanates, e.g. octylisocyanate andoctadecylisocyanate.

Through the following discussion the term isocyanate, for convenience ismeant to include the thio compounds as well as the oxygen containingcompounds unless specifically stated otherwise.

It is well known in the art that isocyanates react with phenolichydroxyl groups, alcoholic hydroxyl groups, and carboxyl groups. Thereaction of a diisocyanate, R (NCO) with an aliphatic or phenolichydroxyl group may be represented as follows:

The reaction established for a diisocyanate and a carboxylic acid, RCOH, is as follows:

It will be seen that if the resinous aryloxy acid contains two or morefunctions of the group, phenolic hydroxyl, alcoholic hydroxyl, andcarboxylic acid, the resulting product will be polymeric. It will alsobe observed that reaction with a carboxylic acid-containing compoundgives carbon dioxide as a by-product, permitting the formation ofcellular structure.

It has'now been found that the reaction of resinous aryloxy acids withpolyisocyanates provides an excellent means of obtaining polymericresinous urethanes which are useful in forming protective coating filmsand foam resin structures. The resinous aryloxy acids possess aplurality of different functional groups reactive with the isocyanatesand have a desirable balance between the content of hydroxyl groups andcarboxyl groups. There is thus provided an optimum combination ofreactive groups facilitating polymerization to an insoluble, infusiblestate and to readily forming foams. The cyclic and aliphatic structurefound in the aryloxy acids employed herein, contribute a desirablecombination of hardness and toughness to the infusible, insolubleurethane products prepared therefrom. The resinous aryloxy acids arecompatible with a large number of other chemicals, including resinoustypes. These compounds may be used in combination with the aryloxy acidsin reactions with the isocyanates to form insoluble, infusible productspossessing widely varying properties.

Through this invention films which are suitable for protective coatingshave been prepared having outstanding properties such as water whiteclarity, extreme toughness and flexibility, and outstanding chemical andwater resistance. A film prepared from a composition of this inventionhas been subjected to 5% alkali at room temperature for over onethousand hours, to boiling water for longer than 12 hours, to boilingtoluene for 1 /2 hours, to room temperature alcohol for 1 hour, to roomtemperature ammonium hydroxide for 1 hour and to room temperaturediethyl ether for 1 hour without any indication of failure. Compositionswith such outstanding characteristics have numerous commercialapplications in the protective coating field. One such application wouldbe in the formulation of white enamel finishes where it is necessary tohave extreme hardness, good chemical and water resistance, exceptionalclarity of film and no unsaturation to cause yellowing of the finish dueto air oxidation. By varying the composition of the acids as well as theisocyanate almost unlimited unique compositions may be obtained.

Foamed resin structures have also been prepared with the resinousaryloxy acids and isocyanates described herein. Cellular structurespossessing outstanding toughness, rigidity, resistance to chemicals andwater, and exceptionally low density have been obtained from thesematerials. Because of this exceptional combination of characteristics,these foamed resin structures have utility in air domes, sandwichedbetween sheets of metal or wood for building blocks, as insulatingmaterials, etc.

The cellular structures of this invention are unique since the gaseousmedium needed to foam the resinous composition is supplied internallythrough the liberation of the CO formed by the reaction of the carboxylgroup with the isocyanate. It is apparent therefore, that no externalfoaming agent is essential. Since the resinous acids have a relativelyhigh molecular weight (approximately 600 to 1400) the foaming action iseasy to control. It should also be noted that because of the use ofexternal heat the entire foaming operation may be com pleted in lessthan one hour. In the present commercial polyurethane foams, in whichwater is used as the sole foaming agent, a post-curing operation ofapproximately 24 hours is needed. The composition and process of thisinvention therefore show substantial advantages over known means. It isbelieved that one outstanding use for the compositions of this inventionwill be as low density, rigid foams possessing a high degree of chemicaland water resistance.

In general the process for preparing the protective coating films asdescribed herein comprises a simple admixing of a solution containingthe aryloxy acids with the isocyanate. The solvent used to out the acidand the isocyanate, when it is desirable to cut the isocyanate, must beinert to the isocyanate and acid. Methyl ethyl ketone is an operablesolvent. The admixtures of the isocyanates and acids have been found tobe stable for a period of 6 to 144 hours. This stability characteristicis of particular importance in industrial applications where theadmixture is made up and used as needed. The films are spread from theseadmixtures and are either air cured or cured at elevated temperatures.If the films are air cured it is preferred that a catalyst such astriethylamine be used to accelerate the reaction.

Strongly basic catalyst such as sodium hydroxide should be avoided sincethe reaction may become explosive. Films can be cured in just a fewminutes at elevated temperatures as illustrated in the examples.

The manufacture of foamed resin structures as herein described comprisesmixing the aryloxy acid with a catalyst in a suitable reaction vessel,raising the temperature to approximately C. or to a temperature wherethe acid is molten, adding the isocyanate while stirirng and allow tofoam. The foamed structure may be heat converted an additional 5 to 30minutes in a suitable draft oven. Although not essential, it isusually-desirable to employ an emulsifier in order to obtain a more homogeneous mixture of the reactants. The instant process may be carired outreadily in any system which provides for stirirng and has sufiicientspace for the foaming action to proceed unhindered. A modification of aunit currently used in commercial urethane foam production may also beemployed. Such a system comprises two supply tanks connected to apressure-mixing nozzle by suitable feed lines. One tank contains theisocyanate and the other tank, necessarily being heated to about G,contains the aryloxy acid emulsified with the emulsifying agent andcatalyst. The aryloxy acid and isocyanate would feed from the tanks tothe nozzle where they would be mixed under pressure and said mixtureflowed into pans and the foaming reaction allowed to proceed unhindered.The foams again may be cured in a suitable draft oven at elevatedtemperatuers thus accelerating the operation.

It has been observed that a wide range of proportions of the reactantsmay be used. Desirable films and foams have been obtained using about10-1 to l-8 ratio of isocyanate to acid on an equivalent basis, withmarked improvement being evident when the equivalent ratio of isocyanateto acid is from about 5:1 to 1:3. It has also been observed that, whilethe above ratios are operable for most practical purposes an even ornear even ratio is the most desired, therefore the preferred ratio ofisocyanate to acid is from about 2:1 to 1:2. The probable explanationwhy such a wide range of proportions can be used is apparently that thearyloxy acid can self-polymerize on application of heat by acondensation reaction and the diisocyanate can polymerize by an additionreaction.

In order to have a guide -in the formulation of these compositions, theamine equivalents of the isocyanates used and the isocyanate equivalentof some of the aryloxy acids were determined. Equivalents as expressedabove are based on the observed amine equivalent of the isocyanate andthe observed or theoretical isocyanate equivalent of the acid. Theanalytical procedure used to determine amine equivalents ofdiisocyanates is found in Monsanto Chemical Companys Technical Bulletin#P-125. Twenty-five milliliters of redistilled toluene and 25 ml. ofapproximately 2 N di-n-butylamine were placed in a carefully cleaned anddried 250 ml. or 500 ml. Erlenmeyer flask. The sample of diisocyanatewas drawn into a warmed glass bulb and the neck sealed off in a flame.Sample weight is determined by the difference. The bulb was immersed inthe Erlenmeyer flask and crushed beneath the surface of the liquid. Thesolution was heated to boiling and allowed to cool one hour. 100 ml. oftechnical methanol and 0.5 ml. of bromophenol blue indicator was added.It was then titrated with 1 N HCl to a yellow end point. The indicatorwas prepared by taking 0.1 g. of bromophenol blue, 1.5 ml. of 0.1 N NaOHdiluted with 100 ml. of distilled H O. The average precisiondemonstrated by these determinations was *-1.29%.

This procedure can be modified to determine isocyanate equivalents ofthe resinous aryloxy acids. The isocyanate equivalent is defined as theweight of an active hydrogen-containing compound which will react withone equivalent of the isocyanate. The method used in determining theobserved values reported is that of reacting a sample of the activehydrogen compound with an excess of toluene-2,4-diisocyanate and thendetermining the excess isocyanate by reaction with di-n-butylamine. To25 ml. of methyl isobutyl ketone was added three grams oftoluene-2,4-diisocyanate previously standardized against di-n-butylamineand a weight of the active hydrogen compound such that the diisocyanateis present in approximately 100% excess. To this mixture is added 1% ofthe total weight of isocyanate and the active hydrogen compound astriethylamine. The mixture is refluxed for a period of one hour. Aftercooling to room temperature, the condenser walls are rinsed with about25 ml. of redistilled toluene. To this mixture is added 25 ml. of 2 Ndi-n-butylamine. This mixture is warmed to the boiling point and allowedto stand for one hour at which point 75 ml. of methanol is added and theexcess di-n-butylamine back-titrated with 1 N alcoholic hydrochloricacid.

In order that those skilled in the art may better understand how thepresent invention may be practiced, the following examples are setfotrh. These examples are presented by way of illustration and not byway of limitation since there are many forms of the invention other thanthese specifically embodied.

Examples I to VII describe the preparation of some typical resinousaryloxy acids which are used in reaction with isocyanates to give thepolyurethane-modified compositions described herein. The quantities ofmaterials are given in parts by weight unless otherwise indicated.

Example I To a solution of 456 parts of p,p-isopropylidenediphenoldissolved in 850 parts of water containing 80 parts of caustic soda wasadded 92.5 parts of epichlorohydrin at 70 C., and with continuousagitation the reaction mixture was raised to approximately 95 C. holdingthis temperature for 1 hour after addition of the epichlorohydrin. Asolution of 189 parts of chloroacetic acid and 160 parts of caustic sodadissolved in 800 parts of water was added and the mixture held at 100 C.for 1 hour at which time 476 parts of 37% hydrochloric acid and 500parts of water were added and the mixture stirred for an additionalhour. The aqueous layer was decanted and the product washed three thimesby stirring one-half hour with 200 parts of hot water, removing thewater each time by decantation. The resin was dried by heating to 130C., giving 565 parts of a product having a softening point of 77 C.

Softening points as used throughout this disclosure were run by DurransMercury Method (Journal of Oil and Color Chemists Association, 12, 1735[1929]). Acid values are defined as the number of milligrams ofpotassium hydroxide which is equivalent to the acid content of one gramof the sample.

Example II To a solution of 456 parts of p,p-isopropylidenediphenoldissolved in 360 parts of water containing 80 parts of caustic soda wasadded 92.5 parts of epichlorohydrin at 60 C., and with continuousagitation the reaction temperature was raised to 95100 C., and held for1 hour after all the epichlorohydrin had been added. To the reactionmixture was added 500 parts of boiling water, the mixture stirred forabout minutes, and the water layer removed by decantation. This waterwashing was repeated twice, saving the washings which were laterneutralized with acid to precipitate unreactedp,p-isopropylidenediphenol. After adding 500 parts of hot water andadjusting the temperature to 90 C., 189 parts of chloroacetic aciddissolved in 300 parts of water containing 80 parts of caustic soda wasadded. The temperature was raised to 80 C., and additional causticsolution of parts caustic soda in 150 parts water was added. Thereaction mixture was heated to 100 C. and held for 1 hour, after whichthe aqueous layer was removed by decantation. To the agitated resinousproduct was added 1,000 parts of hot water and parts of 37% hydrochloricacid, after which the stirring was continued at 95 C. for 45 minutes.The aqueous layer was then removed by decantation, and the resin washedthree times using 2,000 parts hot water for each wash. The resin wasfinally dried by heating with continued agitation to C. to give 841parts of a product having a softening point 87 C., an acid value of 57,an alcoholic hydroxyl value of 110, and a phenolic hydroxyl value of103.

Example III In a caustic solution containing 53 parts caustic soda and402 parts water was dissolved 297 parts of p,p'-isopropylidenediphenol.To this agitated mixture was added 49 parts of epichlorohydrin at 70 C.,and the reaction mixture raised to approximately 95 C., holding thistemperature for 45 minutes after the addition of epichlorohydrin. Asolution of 90 parts chloroacetic acid and 38 parts caustic soda in 288parts water was added and the mixture held at 95 C. for 45 minutes. Tothe reaction mixture was added 18 parts epichlorohydrin, and thereaction mixture was held at 95 C. for an additional 45 minutes at whichtime 104 parts 93% sulfuric acid which had been diluted with 292 partswater was added and stirring was continued for 45 minutes at 95 C.,after which the aqueous layer was removed by decanta tion. The productwas washed three times with hot water and dried by heating to 130 C.This resin had a softening point of 78 C., an acid value of 100, analcoholic hydroxyl value of 97, and a phenolic hydroxyl value of 78.

Example IV To 456 parts of p,p-isopropylidenediphenol dissolved in 800parts of water containing 80 parts of sodium hydroxide was added withcontinuous agitation a mixture containing 75 parts of1,4-dichlorobutene-2, and 25 parts 1,2-dichlorobutene-2 at 56 C. Thereaction mixture was raised to approximately 95 C. and held at thistemperature for 1% hours. With continuous agitation was added 232 partsof sodium chloroacetate in 600 parts of water and 100 parts of sodumhydroxide in 250 parts of water. With continuous agitation heating wascontinued for 1 hour at 95 C. At this point an additional 38 parts ofmixed dichlorobutene was added and heating at 95 C. continued foranadditional hour. The reaction mixture was neutralized with hydrochloricacid and washed and dried as in Example I to give a resinous producthaving an acid value of 116.

Example V A portion of 1140 parts of p,p'-isopropylidenediphenol wasdissolved in 1500 parts of water containing 408 parts of sodiumhydroxide and 573 parts bis(beta-chloroethyl)etl1er was added. Thereaction mixture in a closed system was heated to C. and held at thistemperature for 4 hours with continuous agitation. After the mixture hadcooled to 98 C. the Water layer was removed by decantation and theproduct washed with water three times in the usual manner. Thisintermediate resinous product was dried by heating to 150 C. to give1365 parts of a hard brittle resin. To 355 parts of this resin dissolvedin 600 parts of dimethyl sulfoxide was added 25 parts sodium hydroxidein 200 parts of water. To the constantly agitated mixture at thetemperature of boiling water was added 232 parts of sodium chloroacetatedissolved in 600 parts of water over a period of 30 minutes. Thereaction mixture was heated for an addii nal' 30. nil l esv a 95 Cl Thea i n m x e was neutralized with hydrochloric acid and washed and driedas in Example I to give a pIQduct having an acid value of 35.

Example VI As. Example V a portion of 1026 parts ofp,p-isopropylidenediphenol was dissolved in 1500 parts of watercontaining 325 parts. of sodium hydroxide and 429 parts ofbist'beta-chloroethyl:).ether was placed in a closed re- 10 in- 400parts of water containing 40 parts of sodium hydroXidQ and at. atemperature of 98 C. was added 116 parts of sodium chloroacetatedissolved in 300 parts of water. An additional 20 parts of sodiumhydroxide dissolved in 100 parts of water was added to the reactionmixture. The reaction mixture was continuously agitated for a period of1 hour at 95 C. The alkaline reaction mixture was then neutralized withhydrochloric acid and washed and dried to give 410 parts of a producthaving a softening point of 59 C. and an acid value of 49,.

E z e A portion of 1140 parts 0t p,p' isopropylidenediphenol wasdissolved in 1500 parts ofwater containing 205' parts of sodiumhydroxide and 358 parts of bis(-beta -chloroethyDether and the reactionmixture raised to 150 C. and held at this temperature for 6 hours (aclosed pressure reactor provided with agitation was required for thispreparation). After the mixture had cooled to 98* G. the Water layer wasremoved by decantation and the product washed three times with hot waterin the usual manner. This intermediate resinous-product was dried byheating to 130 C. to give 1275 parts of a hard brittle resin. To 263parts of this resin dissolved in 600 parts of Water containing 40 partsof sodium hydroxide and at a temperature of 98 C; was added- 116 partsofsodium chloroacetate dissolved in 500 parts of water. To this mixturewas added 20 parts of sodium hydroxide in 100 parts of water. Thereaction mixture was continually agitated for 1 hour at 95 C. To themixture was added 14 parts of epiehl'orohydrin and the reactioncontinued with agitation for 1 hour at 95 C. The alkaline reactionmixture was then neutralized with hydrochloric acidand washed and driedin the usual manner to give a product having an acid value of 80.2. Y

A selective list of isocyanates; are given in the table below withabbreviations used in subsequent tables as well as pertinentinformation. Isocyanates other than those listed are operable in thisinvention.

Abbrevia- Amine Equivalent Commercial Source and tions Used StructureTrade Name in Tables Observed Theory E.II. du Pont de Nemours & 00., HyT CH; 90. 62 87.07

Eylene T NC O Toluene 2,4diisocyanat e E. I. du Pont de Nemours & (30.,Hy M H 139. 98 12$. 12

Inc. OCN Hg NCO Hylene M I i Methylene bis (4-phenyl isocyanate)National Aniline Div N 200 Me Me 132. 78 1 32. 13

N aeconate 200 oo ,N O

3,3 Bitolylene 4,4'diisocyan ate Mobay Chemical Co MO HX OCN(CH2)eNCQ103. 39 84. 01

Mondur EX Hexamethylone diiso c yanate Mobay Chemical Co MO 0CHflCHQnNCO 342 32 295. 0

Mondur O Octadecylisocyanate Mobay Chemical Co MO TM CH; 107. 78 123.

Mondur TM CH CH Tritoiymethane triisqeyanate 1 1 Examples VIII throughXXXVII illustrate the preparation of insoluble, infusible protectivecoating films from the aryloxy acids and the isocyanates tabulatedabove. In the preparation of the composition for heat curing to formresistance which was much tougher than the product of Example XXXVIII.

Example XL 16 parts of Example II and 1 part of Tween 81 were protectivecoating films each of the resinous aryloxy acids 6 h d t d b f wasdissolved in methyl ethyl ketone to a nonvolatile gi 2 g g i g y ancontent of 40 to 50%. The isocyanates were used at 100% a d i inonvolatile content. Mixtures of the resinous aryloxy g an measly S i ip 8 acid solutions with the isocyanates were found to be stable g y ensg g ga. an 2 g {16 for periods ranging from 6 to 144 hours. Mixtures of10 Ca i were a h the solutions were spread on panels with a .002" BirdPam a g g h 2 t ea s applicator and the films were baked for periods of5 to if??? ac Ion w 3 W: 9 25? 60 minutes at temperatures ranging from100 to 175 C. n i i was ow ensl 0am Proportions hereinafter expressedrefer to parts by weight z g assible 8 obtain f ams ith Va i d i and arebased on nonvolatile content of the solutions Po o l Hg of reactantsties by simply carrying out the foamlng reaction at dif- Compositions ofthis invention may be air cured as fgi fi g giggi followmg examples W111well as by curing at elevated temperatures. By way of p illustrationExamples VIII, XVI, and XVII were air cured Example XLI at roomtemperature to hard, insoluble, infusible films in 320 parts of ExampleIII, 20 parts of Tween 81, and 2.1 6 to 18 hours when drawn out in thin(.002) films. parts triethylamine catalyst were charged to a stainless Pt Conversion witllistoodin 8.1 S 01115 Aryloxy 'Iriethyl- Example N 0.Acid Parts Isocyanate Parts amine Catalyst Time Temp., 11:02.1; 5% Au.(Hrs) 0. 100 C. NaOH at C.

25 52 2 22 :5 25 1 25 M0 BX 21 .50 120 15 25 125 1 -12 12 :12 :2 21 o 21HY M 14 g5 :12 ii oii '12 175 10 20 21 N200 27 .12 175 16 50 25 MO HX 21.50 125 15 50 21 HYM 28 .12 175 16 50 21 M0 HX 10 1.0 175 1 50 21 Mo HX21 .50 175 1.5 50 a a; 5 5 2 52 *2 29 .5 29 HY M 14 .50 175 10 50 29 HYM 28 .5 175 10 50 52 52 12 5 44 5 44 HY M 22 .50 175 10 50 44 N200 27.50 175 15 5 74 HYM 28 .50 175 2 50 74 N200 27 .50 175 1 50 74 HY'I 1s.50 150 2 50 74 585%. 21 -5 2s 1 12s 74 o 21 HY M .50 150 10 50 63 HYM.50 150 16 50 25 21 161 1 1.0 175 0 24 21 MO TM .50 175 2 2 1 Tests werestopped with no indication of film failure. Examples XXXVIII throughXLIII will illustrate the steel beaker and heated to a temperature of110 C. preparation of foam resin products. When stirred to a homogeneousmixture the resin was Example XXXVIII cast and 9.8 allquot port1ons, forfoaming at varlous temperatures, were charged to open containers. The 16Parts of Example In and 1 P of Tween m aliquot portions were heated withstirring to the given fifactur d by At s Powder p y, a p y y ylenefoaming temperature. 2.9 parts hexamethylene diisosorbitan monooleateemulsifier, were charged to an open cyanate were added and charge againheated to given Container and heated y mean of all 011 bath temperaturewith continued stirring. External heat was At this time the resinousacid was molt n a d 5 removed and foaming allowed to take placeunhindered. 1sltirred. t11.018 pargs triethyltamlne (2211253 551antihilf Pu t Thef dlelrnsity ogfothege fozgrzs at the given tgmperature are exame y 6116 usocyana 6 were a & W1 S llllng. as 0 0W5;gram per cu 1c centimeter- Stirring was continued until the temperaturereached 90 100 C O45 gram per ubi e tim t 110 C C. at which time thecomposition was put in a 100 C. gram per cubic centimeter; 160 C 072gram per bi draft oven for 10 minutes. The product was a low dene ti ete170 C ()8 gram per ubi ti t sity, rigid foam which was very light incolor and had good impact resistance. Example The procedure used is thatof Example XLI with 3.9 16 f E le I fT 81 7 parts mfethlylerliebis(41-1pl11enyldi s ocyanate) being used in parts 0 xamp e I an part 0ween were p ace 0 t e examet yene nsocyanate. The bulking charged to anopen container and the foaming process density in relation totemperature is as follows: C: carried out as in Example XXXVIII using7.0 parts .089 gram per cubic centimeter; C.=.075 gram per methylenebis(4-phenyl isocyanate). The product was cubic centimeter; C.=.074 gramper cubic centia medium low density, rigid foam having good impact 75meter; C.=.056 gram per cubic centimeter;

320 parts of Example VII, 20 parts Tween 81 and 2.1 parts triethyl aminecatalyst were charged to a stainless steel beaker and the materialsheated to 100 C. while stirring to a homogeneous mixture. 9.8 aliquotportions were weighed into open containers and foamed as in Example XLIusing 3.9 parts bis(4-phenyl isocyanate). Densities of products at giventemperatures are as follows: 60 C.=.110 gram per cubic centimeter; 70 C:.100 gram per cubic centimeter; 80 C.=.087 gram per cubic centimeter;120 C.=.085 gram per cubic centimeter; 140 C.=.066 gram per cubiccentimeter; 150 C.=.065 gram per cubic centimeter; 170 C.=.047 gram percubic centimeter; 180 C.=.072 gram per cubic centimeter; 205 C.=.075gram per cubic centimeter.

If it is desired, water can be used to enhance the foaming action ofthese compositions and to permit further variation in their properties.Desirable amounts range up to about 15% based on the total weight of thecomposition.

Example XLIV parts of Example H were charged to an open container and bymeans of an oil bath heated to 85 C. At this time the resinous acid wasmolten and easily stirred. 1 part of Tween 81, 1 part water and .08parts triethylamine catalyst were added with thorough mixing. 7.5 partshexamethylene diisocyanate were then added with stirring. Stirring wascontinued until a temperature of 90 C. was reached at which time thecomposition was put in a 100 C. draft oven for 10 minutes. The productwas a low density foam with good impact resistance.

It should be appreciated that while there are above disclosed but alimited number of embodiments of this invention, it is possible toproduce still other embodiments without departing from the inventiveconcept herein disclosed.

It is claimed and desired to secure by Letters Patent:

1. A composition of matter comprising the reaction product of (A) anorganic polyisocyanate, (B) a phenoxy monocarboxylic acid of the generalformula F "l HOAO-ROAO L l. where A is an arylene radical, R is adivalent aliphatic radical of 2 to 10 carbon atoms, R is a divalentaliphatic hydrocarbon radical of 1 to 7 carbon atoms and n has a valueof 1 to 5, and wherein (A) and (B) are present on an equivalent ratio ofcfrom about 5 :1 to 1:3.

2. The composition of matter as described in claim 1 wherein (A) is anaromatic polyisocyanate.

3. A composition of matter as described in claim 1 wherein (A) is analiphatic polyisocyanate.

4. A composition of matter as described in claim 1 wherein the phenoxymonocarboxylic acid has the structure nndnhasavalueofltoi.

14 5. A composition of matter as described in claim 1 wherein thephenoxy monocarboxylic acid has the structure organic polyisocyanate and(B) a phenoxy monocar boxylic acid of the general formula where A is anarylene radical, R is a divalent aliphatic radical of 2 to 10 carbonatoms, R is a divalent aliphatic hydrocarbon radical of 1 to 7 carbonatoms and n has a value of 1 to 5, and wherein (A) and (B) are presenton an equivalent ratio of from about 5:1 to 1:3.

7. The method of preparing a composition of matter which comprises (1)heating a phenoxy monocarboxylic acid at a temperature sufficient tomelt, said acid having the general formula wherein A is an aryleneradical, R is a divalent aliphatic radical of 2 to 10 carbon atoms, R isa divalent aliphatic hydrocarbon radical of 1 to 7 carbon atoms and nhas a value of 1 to 5, (2) admixing said phenoxy acid with an organicpolyisocyanate, (3) allowing the admixture to storm a cellular structureby the release of carbon dioxide from the reaction of the acid with theisocyanate, and (4) curing said cellular structure by heating to -175 C.for 5 to 60 minutes, the equivalent ratio of the phenoxy monocarboxylicacid to organic polyisocyanate being from 5 :1 to 1:3.

References Cited in the file of this patent UNITED STATES PATENTS2,444,594 Day et al July 6, 1948 2,594,979 Nelson Apr. 29, 19522,788,335 Barthel Apr. 9, 1957 FOREIGN PATENTS 901,768 France Nov. 13,1944 652,030 Great Britain Apr. 11, 1951

7. THE METHOD OF PREPARING A COMPOSITION OF MATTER WHICH COMPRISES (1)HEATING A PHENOXY MONOCARBOXYLIC ACID AT A TEMPERATURE SUFFICIENT TOMELT, SAID ACID HAVING THE GENERAL FORMULA